Many viscosifiers for, and methods of, increasing the viscosity of aqueous liquids are known. Such viscosifiers may be so-called water-soluble polymers such as biopolymers, gums, cellulose derivatives, alginates, and other polysaccharides or polysaccharide derivatives, and various synthetic polymers. Representative polymers are set forth in the book "Handbook of Water Soluble Gums and Resins," Robert L. Davidson, Ed., 1980.
Noticeably absent from this book is any mention of chitosan or derivatives thereof
Viscoelastic fluids are characterized as having a Theological profile which is shear thinning, having a high viscosity at extremely low shear rates and a low viscosity at high shear rates. Thus such fluids are pseudoplastic having a high yield stress.
This type of rheology is produced by hydrating in the fluid certain water soluble polymers. These polymers presently known are biopolymers, i.e., microbially produced polysaccharides or heteropolysaccharides, and are well known in the art.
There is a need for fluids which exhibit a high low shear rate viscosity which are shear thinning.
Chitosan is a partially or fully deacetylated form of chitin, a naturally occurring polysaccharide. Structurally, chitin is a polysaccharide consisting of beta-(1.fwdarw.4)2-acetanido-2-deoxy-D-glucose units, some of which are deacetylated. The degree of deacetylation usually varies between 8 and 15 percent, but depends on the species from which the chitin is obtained, and the method used for isolation and purification.
Chitin is not one polymer with a fixed stoichiometry, but a class of polymers of N-acetylglucosamine with different crystal structures and degrees of deacetylation, and with fairly large variability from species to species. The polysaccharide obtained by more extensive deacetylation of chitin is chitosan.
Like chitin, chitosan is a generic term for a group of polymers of acetylglucosamine, but with a degree of deacetylation of between 50 and 100 percent. Chitosan is the beta-(1-4)-polysaccharide of D-glucamine, and is structurally similar to cellulose, except that the C-2 hydroxyl group in celullose is substituted with a primary amine group in chitosan. The large number of free amine groups (pKa=6.3) makes chitosan a polymeric weak base. Both chitin and chitosan are insoluble in water, dilute aqueous bases, and most organic solvents. However, unlike chitin, chitosan is soluble in dilute aqueous acids, usually carboxylic acids, as the chitosonium salt. Solubility in dilute aqueous acid is therefore a simple way to distinguish chitin from chitosan.
Chitosan is unique in that it is a polysaccbaride containing primary amine groups. Chitosan forms water-soluble salts with many organic and inorganic acids.
It is known to prepare chitosan derivatives by attaching various groups to one or more hydroxyl groups of the chitosan, as in various cellulose derivatives, and/or in attaching various groups to the primary amino group of chitosan. Thus it is disclosed in Hall and Yalpani U.S. Pat. No. 4,424,346 that chitosan can be reacted with various aldehydes by Schiff base formation with the primary amino group. The reaction is conducted in the presence of a reducing agent, specifically sodium cyanoborohydride, to reduce the amino group formed to a secondary amino group, i.e., the chitosan undergoes reductive alkylation. The aldehyde reactants include aldose or ketose sugars, or sugars oxidizable or hydrolyzable to aldoses or ketoses, for example, glucose, galactose, arabinose, xylose, N-acetylglucosamine, lactose, cellobiose, maltose, and melibiose, and aromatic aldehydes containing at least one hydroxyl or carboxyl group. A paper which discusses the preparation and characteristics of the chitosan derivatives set forth in the Hall et al. U.S. Pat. No. 4,424,346 is "Some Chemical and Analytical Aspects of Polysaccharide Modifications. 3. Formation of Branched-Chain, Soluble Chitosan Derivatives," M. Yalpani and L. D. Hall, MACROMOLECULES 1984, 17, 272-281. These chitosan derivatives are disclosed to offer a wide range of solubility, gelling and compatibility properties.
A paper entitled "Chitosan Derivatives Bearing C.sub.10 -Alkyl Glycoside Branches: A Temperature-Induced Geiling Polysaccharide," K. R. Holme and L. D. Hall, Macromolecules 1991, 24, 3828-3833, discloses chitosan derivatives having mixed hydrophobic/hydrophilic branches.
U.S. Pat. No. 3,879,376, incorporated herein by reference, discloses chitosan derivatives formed by acylation of chitosan with a saturated or unsaturated organic diacid anhydride and their use as a skin-moisturizing agent in cosmetic compositions.
There is disclosed in co-pending U.S. patent application Ser. No. 09/222,293 filed Dec. 28, 1998, well drilling fluids containing chitosan and aldose or ketose sugars, and/or oligosaccharides of such sugars.